Olefin polymerization catalyst system

ABSTRACT

This invention relates to an olefin polymerization catalyst composition comprising the product of the combination of an activator, an additive and a transition metal compound which is represented by the formulae: 
     
       
         ((Z)XA t (YJ)) q MQ n   
       
     
     where M is a metal selected from Group 3 to 13 or lanthanide and actinide series of the Periodic Table of Elements; Q is bonded to M and each Q is a monovalent, divalent or trivalent anion; X and Y are bonded to M; X and Y are independently carbon or a heteroatom, provided that at least one of X and Y is a heteroatom, preferably both X and Y are heteroatoms; Y is contained in a heterocyclic ring J, where J comprises from 2 to 50 non-hydrogen atoms, Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms; t is 0 or 1; when t is 1, A is a bridging group joined to at least one of X, Y or J, q is 1 or 2; n is the oxidation state of M minus q if Q is a monovalent anion, n is (the oxidation state of M−q)/2, if Q is a bivalent anion or n is (the oxidation state of M−q)/3 if Q is a trivalent anion, optionally R′ m  may be bound to Z and /or R″ p  may be bound to J 
     the R″ groups are independently selected from the group consisting of hydrogen or linear, branched, cyclic, alkyl radicals, or alkenyl, alkynyl, alkoxy, aryl or aryloxy radicals, two or more R″ groups may be joined to form a cyclic moiety, m is an integer from 0 to 5, preferably 2; 
     the R′ groups are independently selected from group consisting of hydrogen or linear, branched, alkyl radicals or cyclic alkyl, alkenyl, alkynyl or aryl radicals; two or more R′ groups may be joined to form a cyclic moiety, p is an integer from 0 to 5, preferably 2, 
     and wherein the additive is an alkoxy compound.

STATEMENT OF RELATED APPLICATIONS

This application relates to U.S. Ser. No. 09/103,620 filed Jun. 23, 1998now U.S. Pat. No. 6,103,657 claiming the benefit of provisionalapplication No. 60/051,581, filed Jul. 2, 1997 and to concurrently filedU.S. patent applications, Ser. Nos., 09/213,627, 09/215,706, and09/216,163, all filed Dec. 18, 1998.

FIELD OF THE INVENTION

This invention relates to olefin polymerization catalysts based upontransition metal compounds comprising bidentate ligands containingpyridine or quinoline moieties combined with activators and an additive.

BACKGROUND OF THE INVENTION

The intense commercialization o f metallocene polyolefin catalysts hasled to widespread interest in the design of non-metallocene, homogeneouscatalysts. This field is more than an academic curiosity as new,non-metallocene catalysts may provide an easier pathway to currentlyavailable products and may also provide product and processopportunities which are beyond the capability of metallocene catalysts.In addition, certain non-cyclopentadienyl ligands may be more economicaldue to the relative ease of synthesis of a variety of substitutedanalogs.

Thus there is a need in the art for new novel olefin polymerizationcatalysts. U.S. Ser. No. 09/103,620 discloses the use of transitionmetal compounds comprising bidentate ligands containing pyridine orquinoline moieties and mixtures thereof with activators to polymerizeolefins. In particular [[1-(2-Pyridyl)N-1-Methylethyl]-[1-N-2,6-Diisopropylphenyl Amido]][2-Methyl-1-Phenyl-2-Propoxy] ZirconiumDibenzyl is combined with modified methyl alumoxane in the gas phase toproduce ethylene hexene copolymers.

We have found that the systems in U.S. Ser. No. 09/103,620 U.S. Pat. No.6,103,657 can be modified by the direct addition of an additive toproduce bimodal products from a single catalyst.

For U.S. purposes the following references are mentioned: U.S. Pat. Nos.4,845,067; 4,999,327; JP 1126111; U.S. Pat. No. 4,508,842; and UK1015054.

SUMMARY OF THE INVENTION

This invention relates to an olefin polymerization catalyst systemcomprising the product of the combination of an activator, an additiveand a transition metal compound based on bidentate ligands containingpyridine or quinoline moieties, such as those described in U.S.application Ser. No. 09/103,620 filed Jun 23, 1998, now U.S. Pat. No.6,103,657 which is herein incorporated by reference. This inventionfurther relates to a process to produce polyolefins using suchcatalysts. This invention further relates to resins produced by suchcatalyst system, preferably polyethylene resins, more preferably bimodalhigh density polyethylene resins.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to olefin polymerization catalyst systemcomprising an activator, an additive and a transition metal compoundbased on bidentate ligands containing pyridine or quinoline moieties.

The activator may be any known catalyst activator and in one embodimentis an alkyl aluminum, an alumoxane, a modified alumoxane, apolyalumoxane, a non-coordinating anion, a Lewis acid or a mixturethereof

There are a variety of methods for preparing alumoxane and modifiedalumoxanes, non-limiting examples of which are described in U.S. Pat.Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734,4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801,5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838,5,731,253 and 5,731,451 and European publications EP-A-0 561 476,EP-B1-0 279 586 and EP-A-0 594-218, and PCT publication WO 94/10180, allof which are herein fully incorporated by reference.

Ionizing compounds (non-coordinating anions) may contain an activeproton, or some other cation associated with but not coordinated to oronly loosely coordinated to the remaining ion of the ionizing compound.Such compounds and the like are described in European publicationsEP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-A-0 426 637, EP-A-500944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Pat. Nos. 5,153,157,5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,387,568, 5,384,299 and5,502,124 and U.S. patent application Ser. No. 08/285,380, filed Aug. 3,1994, now abandoned all of which are herein fully incorporated byreference. Other activators include those described in PCT publicationWO 98/07515 such as tris (2, 2′, 2″-nonafluorobiphenyl) fluoroaluminate,which is fully incorporated herein by reference. Combinations ofactivators are also contemplated by the invention, for example,alumoxanes and ionizing activators in combinations, see for example, PCTpublications WO 94/07928 and WO 95/14044 and U.S. Pat. Nos. 5,153,157and 5,453,410 all of which are herein fully incorporated by reference.Also, methods of activation such as using radiation and the like arealso contemplated as activators for the purposes of this invention. Theadditive may be an alkoxy compound. Alkoxy compound is defined to becompounds represented by the formula R═O where R is a C₁ to C₁₀₀ groupand the oxygen may be bound at any point along the R group. The R groupmay also contain heteroatoms, in addition to the 1 to 100 carbon atoms.Preferred alkoxy compounds include ketones and aldehydes. Particularlypreferred alkoxy compounds include acetone, benzophenone, methyl ethylketone, diethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone,diisopropyl ketone, methyl tertiary butyl ketone, acetophenone,cyclohexanone, cyclopentanone, benzaldehyde, pivaldehyde, ethyl n-propylketone, ethyl isopropyl ketone, and the like.

In one embodiment, the transition metal catalyst compound based onbidentate ligands containing pyridine or quinoline moieties isrepresented by the formula:

((Z)XA_(t)(YJ))_(q)MQ_(n)  (I)

where M is a metal selected from Group 3 to 13 or lanthanide andactinide series of the Periodic Table of Elements; Q is bonded to M andeach Q is a monovalent, divalent or trivalent anion; X and Y are bondedto M; X and Y are independently carbon or a heteroatom, provided that atleast one of X and Y is a heteroatom, preferably both X and Y areheteroatoms; Y is contained in a heterocyclic ring J, where J comprisesfrom 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbon atoms; Z isbonded to X where Z comprises 1 to 50 non-hydrogen atoms, preferably 1to 50 carbon atoms or a silyl group, an alkyl silyl group such as atrialkyl silyl, preferably Z is a cyclic group containing 3 to 50 atoms,preferably 3 to 30 carbon atoms; t is 0 or 1; when t is 1, A is abridging group joined to at least one of X, Y or J, preferably X and J;q is 1 or 2; n is the oxidation state of M minus q if Q is a monovalentanion, n is (the oxidation state of M−q)/2, if Q is a bivalent anion orn is (the oxidation state of M−q)/3 if Q is a trivalent anion.,typically n is an integer from 1 to 4 depending on the oxidation stateof M. In one embodiment, if X is oxygen or sulfur then Z is optional. Inanother embodiment, if X is nitrogen or phosphorous then Z is present.In an embodiment, Z is preferably an aryl group, more preferably asubstituted aryl group.

In another embodiment, R′m is bound to Z and R″p is bound to J, the R″groups are independently selected from the group consisting of hydrogenor linear, branched, cyclic, alkyl radicals, or alkenyl, alkynyl,alkoxy, aryl or aryloxy radicals. Also, two or more R″ groups may bejoined to form a cyclic moiety such as an aliphatic or aromatic ring.Preferably R″ is hydrogen or an aryl group, most preferably R″ ishydrogen. When R″ is an aryl group and Y is nitrogen, a quinoline groupis formed. Optionally, an R″ may be joined to A; m is an integer from 0to 5, preferably 2;

the R′ groups are independently selected from group consisting ofhydrogen or linear, branched, alkyl radicals or cyclic alkyl, alkenyl,alkynyl or aryl radicals. Also, two or more R′ groups may be joined toform a cyclic moiety such as an aliphatic or aromatic ring. PreferablyR′ is an alkyl group having from 1 to 20 carbon atoms, more preferablyR′ is methyl, ethyl, propyl, butyl, pentyl and the like, includingisomers thereof, more preferably R′ is a methyl group, or a primary,secondary or tertiary hydrocarbon, including isopropyl, t-butyl and thelike, most preferably R′ is an isopropyl group. Optionally, an R′ groupmay be joined to A. It is preferred that at least one R′ is ortho to X;p is an integer from 0 to 5, preferably 2.

In a preferred embodiment M is a Group 4 to 12 transition metal, morepreferably a Group 4, 5 or 6 transition metal, even more preferably aGroup 4 transition metal such as titanium, zirconium or hafnium, andmost preferably zirconium.

In a preferred embodiment each Q is independently selected from thegroup consisting of halogens, hydrogen, alkyl, aryl, alkenyl, alkylaryl,arylalkyl, hydrocarboxy or phenoxy radicals having 1-20 carbon atoms.Each Q may also be amides, phosphides, sulfides, silylalkyls,diketonates, and carboxylates. Optionally, each Q may contain one ormore heteroatoms, more preferably each Q is selected from the groupconsisting of halides, alkyl radicals and arylalkyl radicals. Mostpreferably, each Q is selected from the group consisting of arylalkylradicals such as benzyl.

In a preferred embodiment, X and Y are independently selected from thegroup consisting of nitrogen, oxygen, sulfur and phosphorous, even morepreferably nitrogen or phosphorous, and most preferably nitrogen.

J contains preferably from 2 to 7 carbon atoms, more preferably from 3to 6 carbon atoms, and most preferably 5 carbon atoms. Optionally, theheterocyclic ring J containing Y, may contain additional heteroatoms.

Z is preferably a hydrocarbyl group bonded to X, preferably Z is ahydrocarbyl group of from 1 to 50 carbon atoms, preferably Z is a cyclicgroup having from 3 to 30 carbon atoms, preferably Z is a substituted orunsubstituted cyclic group containing from 3 to 30 carbon atoms,optionally including one or more heteroatoms, more preferably Z is anaryl group, most preferably a substituted aryl group in anotherembodiment Z may be silyl or an alkyl silyl, preferably a trialkylsilyl.

A is preferably a bridging group containing one or more Group 13 to 16elements from the Periodic Table of Elements. More preferably A containsone or more Group 14 elements, most preferably A is a substituted carbongroup, a di-substituted carbon group or vinyl group.

In a preferred embodiment Q is not a hydrocarboxy or phenoxy radicals.

In one embodiment J is pyridine in any of the above formulae.

The transition metal compounds may be made by any means in the art.

In a preferred embodiment the additive is combined with the transitionmetal catalyst compound in an amount of 0.5 weight % to about 90 weight% based upon the weight of the transition metal catalyst compound andthe additive, but not any activators or supports, preferably 1 weight %to about 80 weight %, more preferably 10 to 60 weight %.

The additive may be combined with the transition metal catalyst compound(with or without the activator) before being added to the polymerizationreactor. In one embodiment the additive is added to the transition metalcatalyst compound in line in the injection tube.

In a preferred embodiment the activator is allowed to react with thetransition metal catalyst compound (that has already bee reacted withthe additive) for at least 5 minutes before being combined with theolefin, preferably 10 minutes, more preferably 15 minutes. It has beennoted that if the transition metal catalyst compound is simply combinedwith the additive then added directly to the reactor, that less bimodalproduct is obtained. If the additive and the transition metal compoundare allowed to react then for a period of time then more bimodal productis obtained.

In another preferred embodiment the activator and the transition metalcatalyst compound are combined in a ratio of 0.5 to 1 to 10,000 to 1,more preferably 1 to 1 to 1000 to 1, more preferably 100 to 1 to 500 to1.

In a preferred embodiment the additive and the transition metal catalystcompound are combined prior to being combined with the activator. In aalternative embodiment the transition metal catalyst, olefin and theactivator are already present in the polymerization reactor and theadditive is added. In embodiments where the additive is to be addedafter the activator and the transition metal catalyst compound arealready combined and the activator is alumoxane, then extra amounts ofadditive may be required.

Different additives may be used to achieve different effects on thepolymer produced. For example using diethyl ketone as the additiveproduces a polymer having a higher molecular weight than does usingmethyl ethyl ketone as the additive. Likewise using methyl ethyl ketoneas the additive produces a polymer having a higher molecular weight thanusing acetone as the additive does.

In a preferred embodiment the transition metal catalyst compound,[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl Amido]Zirconium Tribenzyl and the additive acetone are used in combinationwith an alumoxane, preferably a methyl alumoxane, more preferably amodified methyl alumoxane in a gas phase or slurry reactor to producepolyethylene, preferably high density polyethylene. In another preferredembodiment a non-coordinating anion, such as tri (n-butyl) ammoniumtetrakis (pentafluorophenyl) boron or a trisperfluorophenyl boron, isused in combination with the transition metal catalyst compound,[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl Amido]Zirconium Tribenzyl and acetone, in a gas phase or slurry phase reactor.

The additive may or may not be present when the activator is added tothe transition metal compound before or after being placed in thereactor.

Likewise the transition metal catalyst compound, the activators, orcomponents thereof may be supported on an organic or inorganic support.Typically the support can be of any of the solid, porous supports.Typical support materials include talc; inorganic oxides such as silica,magnesium chloride, alumina, silica-alumina; polymeric supports such aspolyethylene, polypropylene, polystyrene; and the like. Preferredsupports include silica, clay, talc magnesium chloride and the like.Preferably the support is used in finely divided form. Prior to use thesupport is preferably partially or completely dehydrated. Thedehydration may be done physically by calcining or by chemicallyconverting all or part of the active hydroxyls. For more information onhow to support catalysts please see U.S. Pat. No. 4,808,561 whichteaches how to support a metallocene catalyst system. The techniquesused therein are generally applicable for this invention. In oneembodiment the transition metal compound is placed upon a support thenthe additive is added and allowed to react for at least 10 minutes,thereafter the activator is added combined with the supported transitionmetal compound.

The transition metal catalyst compound and/or the activator may beplaced on separate supports or may be placed on the same support andthereafter treated with the activator. The catalysts/catalyst systemsand/or their components need not be feed into the reactor in the samemanner. For example, one catalyst or its components may slurried intothe reactor on a support while the other catalyst or components areprovided in a solution.

In another preferred embodiment two different transition metal compoundsare used in combination with an activator and an additive in the samereactor.

In another embodiment two reactors are used in series and a differenttransition metal catalyst compound is placed in each with the same ordifferent activators and an additive is added to at least one reactor.

In a preferred embodiment the catalyst system is fed into the reactor ina solution or slurry. Hydrocarbons are useful for the solutions orslurries. For example the solution can be toluene, hexane, isopentane ora combination thereof such as toluene and isopentane or toluene andpentane. A typical solution would be 0.02 to 0.05 mole catalyst in thehydrocarbon carrier, preferably isopentane or hexane.

In another embodiment the carrier for the catalyst system or itscomponents is a super critical fluid, such as ethane or propane. Formore information on supercritical fluids as catalyst feed agents see EP0 764 665 A2.

In another preferred embodiment the one or all of the catalysts arecombined with up to 6 weight % of a metal stearate, (preferably aaluminum stearate, more preferably aluminum distearate) based upon theweight of the catalyst, any support and the stearate, preferably 2 to 3weight %. In an alternate embodiment a solution of the metal stearate isfed into the reactor. These agents may be dry tumbled with the catalystor may be fed into the reactor in a solution with or without thecatalyst system or its components. In a preferred embodiment thecatalysts combined with the activators are tumbled with 1 weight % ofaluminum distearate and/or 2 weight % of an antistat, such as amethoxylated amine, such as Witco's Kemamine AS-990 from ICI Specialtiesin Bloomington Del. The metal stearate and/or the anti-static agent maybe slurried into the reactor in mineral oil or ground into a powder thensuspended in mineral oil then fed into the reactor, or blown directlyinto the reactor as a powder.

More information on using aluminum stearate type additives may be foundin U.S. Ser. No. 09/113,216 filed Jul. 10, 1998, which is incorporatedby reference herein.

In another embodiment the transition metal catalyst compound andactivator are fed into the reactor separately from the additive.

Without wishing to be bound by any theory, is appears that the additivereacts with the transition metal catalyst compound to provide anotheractive catalyst species.

In embodiments of the invention, it has been noted that temperatureaffects the balance between the two forms of the catalyst. It seems thathigher temperatures drive the conversion of the transition metalcatalyst compound in the presence of the additive to the second catalystspecies. Thus by selecting the amount of additive and the temperature atwhich they are combined and/or used one can select for desired endproducts.

Polymerization Process of the Invention

The catalysts and catalyst systems described above are suitable for usea solution, gas or slurry polymerization process or a combinationthereof, most preferably a gas or slurry phase polymerization process.

In one embodiment, this invention is directed toward the solution,slurry or gas phase polymerization reactions involving thepolymerization of one or more of monomers having from 2 to 30 carbonatoms, preferably 2-12 carbon atoms, and more preferably 2 to 8 carbonatoms. Preferred monomers include one or more of ethylene, propylene,butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1,decene-1,3-methyl-pentene-1, and cyclic olefins or a combinationthereof. Other monomers can include vinyl monomers, diolefins such asdienes, polyenes, norbomene, norbornadiene monomers. Preferably ahomopolymer of ethylene is produced. In another embodiment, a copolymerof ethylene and one or more of the monomers listed above is produced.

In another embodiment ethylene or propylene is polymerized with at leasttwo different comonomers to form a terpolymer. The preferred comonomersare a combination of alpha-olefin monomers having 4 to 10 carbon atoms,more preferably 4 to 8 carbon atoms, optionally with at least one dienemonomer. The preferred terpolymers include the combinations such asethylene/butene-1/hexene-1, ethylene/propylene/butene-1,propylene/ethylene/hexene-1, ethylene/propylene/norbornene and the like.

In a particularly preferred embodiment the process of the inventionrelates to the polymerization of ethylene and at least one comonomerhaving from 4 to 8 carbon atoms, preferably 4 to 7 carbon atoms.Particularly, the comonomers arebutene-1,4-methyl-pentene-1,3-methyl-pentene-1, hexene-1 and octene-1,the most preferred being hexene-1 and butene-1.

Typically in a gas phase polymerization process a continuous cycle isemployed where in one part of the cycle of a reactor system, a cyclinggas stream, otherwise known as a recycle stream or fluidizing medium, isheated in the reactor by the heat of polymerization. This heat isremoved from the recycle composition in another part of the cycle by acooling system external to the reactor. Generally, in a gas fluidizedbed process for producing polymers, a gaseous stream containing one ormore monomers is continuously cycled through a fluidized bed in thepresence of a catalyst under reactive conditions. The gaseous stream iswithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product is withdrawn from the reactor and freshmonomer is added to replace the polymerized monomer. (See for exampleU.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749,5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228 allof which are fully incorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 10 psig(69 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in the gas phase process may vary from about 30°C to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C.

The productivity of the catalyst or catalyst system in a gas phasesystem is influenced by the main monomer partial pressure. The preferredmole percent of the main monomer, ethylene or propylene, preferablyethylene, is from about 25 to 90 mole percent and the monomer partialpressure is in the range of from about 75 psia (517 kPa) to about 300psia (2069 kPa), which are typical conditions in a gas phasepolymerization process.

In a preferred embodiment, the reactor utilized in the present inventionis capable and the process of the invention is producing greater than500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), evenmore preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still morepreferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even morepreferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferablygreater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr(45,500 Kg/hr).

Other gas phase processes contemplated by the process of the inventioninclude those described in U.S. Pat. Nos. 5,627,242, 5,665,818 and5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202 andEP-B-634 421 all of which are herein fully incorporated by reference.

A slurry polymerization process generally uses pressures in the range offrom about 1 to about 50 atmospheres and even greater and temperaturesin the range of 0° C. to about 120° C. In a slurry polymerization, asuspension of solid, particulate polymer is formed in a liquidpolymerization diluent medium to which ethylene and comonomers alongwith catalyst are added. The suspension including diluent isintermittently or continuously removed from the reactor where thevolatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

In one embodiment, a preferred polymerization technique of the inventionis referred to as a particle form polymerization, or a slurry processwhere the temperature is kept below the temperature at which the polymergoes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 185° F. (85° C.) toabout 230° F. (110° C.). Two preferred polymerization methods for theslurry process are those employing a loop reactor and those utilizing aplurality of stirred reactors in series, parallel, or combinationsthereof Non-limiting examples of slurry processes include continuousloop or stirred tank processes. Also, other examples of slurry processesare described in U.S. Pat. No. 4,613,484, which is herein fullyincorporated by reference.

In another embodiment, the slurry process is carried out continuously ina loop reactor. The catalyst as a slurry in isobutane or as a dry freeflowing powder is injected regularly to the reactor loop, which isitself filled with circulating slurry of growing polymer particles in adiluent of isobutane containing monomer and comonomer. Hydrogen,optionally, may be added as a molecular weight control. The reactor ismaintained at pressure of about 525 psig to 625 psig (3620 kPa to 4309kPa) and at a temperature in the range of about 140° F. to about 220° F.(about 60° C. to about 104 ° C.) depending on the desired polymerdensity. Reaction heat is removed through the loop wall since much ofthe reactor is in the form of a double-jacketed pipe. The slurry isallowed to exit the reactor at regular intervals or continuously to aheated low pressure flash vessel, rotary dryer and a nitrogen purgecolumn in sequence for removal of the isobutane diluent and allunreacted monomer and comonomers. The resulting hydrocarbon free powderis then compounded for use in various applications.

In another embodiment, the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg /r).

In another embodiment in the slurry process of the invention the totalreactor pressure is in the range of from 400 psig (2758 kPa) to 800 psig(5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig (4827 kPa),more preferably 500 psig (3448 kPa) to about 650 psig (4482 kPa), mostpreferably from about 525 psig (3620 kPa) to 625 psig (4309 kPa).

In yet another embodiment in the slurry process of the invention theconcentration of ethylene in the reactor liquid medium is in the rangeof from about 1 to 10 weight percent, preferably from about 2 to about 7weight percent, more preferably from about 2.5 to about 6 weightpercent, most preferably from about 3 to about 6 weight percent. Anotherprocess of the invention is where the process, preferably a slurry orgas phase process is operated in the absence of or essentially free ofany scavengers, such as triethylaluminum, trimethylaluminum,tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminumchloride, dibutyl zinc and the like. This process is described in PCTpublication WO 96/08520 and U.S. Pat. No. 5,712,352, which are hereinfully incorporated by reference.

In another embodiment the process is run with scavengers. Typicalscavengers include trimethyl aluminum, tri-isobutyl aluminum and anexcess of alumoxane or modified alumoxane.

The proportions of the components of the feed catalyst solution can bevaried to alter molecular weight and other properties. Another method toalter the molecular weight is to add hydrogen to the system byincreasing the hydrogen ethylene ratio. A method to control the densityis altering the comonomer content.

A method to control molecular weight distribution (Mw/Mn), flow index,and/or density comprising altering on line in a commercial scale gasphase reactor (i.e. having a volume of 1500 cubic feet or more) thereaction temp and/or the catalyst ratio in the intimately mixed catalystsolution and/or the hydrogen concentration and/or the activator totransition metal ratio, such as the aluminum/zirconium ratio is alsoprovided herein.

Injection and mixing temperatures also provide a means to alter productproperties as temperature affects activation and/or solvent evaporationand thus alters the catalyst composition and hence alters the finalproduct.

The sequence and timing of activation also provides an opportunity toalter the catalyst composition and thus the final product. For examplehigher concentrations of methyl alumoxane in a system comprising (A).[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl Amido]Zirconium Tribenzyl will alter the balance of Mw species formed by thecatalyst. This includes higher concentrations during activation and/ormixing and/or transport and/or in spraying into the reactor. Likewise wehave noted that increasing the hydrocarbon carrier in the catalyst feedincreased the amount of lower molecular weight fraction produced.

One can also vary the product by altering the reaction temperature. Wehave noted that raising the reaction temperature increased the amount ofthe higher molecular weight component and unusually the two modes in thesize exclusion chromatography graph moved closer together (that is theMw/Mn became lower when compared to the same system at a lowertemperature).

One can also vary the molecular weight distribution by varying thereactor temperature, varying the temperature of the catalyst systembefore it enters the reactor, varying the catalyst to activator ratio,varying the volume of the carrier, and/or contacting the transitionmetal component with solvent prior to activation with the activator. Inanother preferred embodiment the catalyst system in is liquid form andis introduced into the reactor into a resin particle lean zone. Forinformation on how to introduce a liquid catalyst system into afluidized bed polymerization into a particle lean zone, please see U.S.Pat. No. 5,693,727, which is incorporated by reference herein.

In a preferred embodiment, the polyolefin recovered typically has a meltindex as measured by ASTM D-1238, Condition E, at 190° C. of 1g/10 minor less. In a preferred embodiment the polyolefin is ethylenehomopolymer or copolymer. The comonomer is preferably a C3 to C20 linearbranched or cyclic monomer, and in one embodiment is a C3 to C12 linearor branched alpha-olefin, preferably propylene, hexene, pentene, hexene,heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-1,3-methylpentene-1,3,5,5-trimethyl hexene 1, and the like.

In a preferred embodiment the catalyst system described above is used tomake a high density polyethylene having a density of between 0.925 and0.0950 g/cm³ (as measured by ASTM 2839), a melt index of 1.0 or lessg/10 min or less (as measured by ASTM D-1238, Condition E, at 190° C.).

In another preferred embodiment the polyolefin produced has apolydispersity (Mw/Mn) of greater than 5, preferably greater than 7,preferably greater than 9, preferably greater than 12.

In another preferred embodiment the polyolefin produced is bimodal. Bybimodal is meant that the GPC graph of the polymer molecular weightdistribution shows two peaks, or a peak with a hump. Alternately, thepolymer is found to have at least two species of molecular weightspresent at greater than 20 weight % based upon the weight of thepolymer.

The polyolefins then can be made into films, molded articles, sheets andthe like. The films may be formed by any of the conventional techniqueknown in the art including extrusion, co-extrusion, lamination, blowingand casting. The film may be obtained by the flat film or tubularprocess which may be followed by orientation in an uniaxial direction orin two mutually perpendicular directions in the plane of the film to thesame or different extents. Particularly preferred methods to form thepolymers into films include extrusion or coextrusion on a blown or castfilm line.

The films produced may further contain additives such as slip,antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers,antistats, polymer processing aids, neutralizers, lubricants,surfactants, pigments, dyes and nucleating agents. Preferred additivesinclude silicon dioxide, synthetic silica, titanium dioxide,polydimethylsiloxane, calcium carbonate, metal stearates, calciumstearate, zinc stearate, talc, BaSO₄, diatomaceous earth, wax, carbonblack, flame retarding additives, low molecular weight resins, glassbeads and the like. The additives may be present in the typicallyeffective amounts well known in the art, such as 0.001 weight % to 10weight %.

EXAMPLES

MFR Melt Flow Ratio was measured by ASTM 1238.

BBF (butyl branch frequency per 1000 carbon atoms) was measured byinfrared spectroscopy as describe in U.S. Pat. No. 5,527,752.

PDI (polydispersity index) is Mw,/Mn and was measured by Size ExclusionChromotography.

Melt Index (MI) was measured by the procedure according to ASTM 1238,condition E.

Melt Index Ratio (MIR) is the ratio of I₂₁ over I₂ as measured by theprocedure according to ASTM D 1238.

Density is measured according to ASTMD 1505.

MMAO 3A is modified methyl alumoxane commercially available from AkzoChemicals, Inc. under the trade name Modified Methylalumoxane type 3A,covered under patent number U.S. Pat. No. 5,041,584)

Example 1 Preparation of[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl]Amine

In a dry box, 22.45 mmol (6.34 g)2-acetylpyridine(2,6-diisopropylphenylimine) were charged to a 250 mlround bottom flask equipped with a stir bar and septa. The flask wassealed, removed from the dry box and placed under nitrogen purge. Drytoluene (50 ml) was added and stirred to dissolve the ligand. The vesselwas chilled to 0° C. in a wet ice bath. Trimethyl aluminum (Aldrich, 2.0M in toluene) was added dropwise over ten minutes. The temperature ofthe reaction was not allowed to exceed 10° C. When addition of thetrimethyl aluminum was complete, the mixture was allowed to warm slowlyto room temperature, and then was then placed in an oil bath and heatedto 40° C. for 25 minutes. The vessel was removed from the oil bath andplaced in an ice bath. A dropping funnel containing 100 ml of 5% KOH wasattached to the flask. The caustic was charged to the reaction dropwiseover a 1 hour span. The mixture was transferred to a separatory funnel.The aqueous layer was removed. The solvent layer was washed with 100 mlwater then 100 ml brine. The red-brown liquid product was dried overNa₂SO₄, vacuum stripped and placed under high vacuum over night.

80 ml of red-brown liquid was transferred to a 200 ml Schlenk flaskequipped with a stir bar. A distillation head with a dry ice condenserwas attached to the flask. The mixture was vacuum distilled yieldingapproximately 70 g of dark yellow viscous liquid product.

Example 2 Preparation of[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl Amido]Zirconium Tribenzyl

In a darkened room and darkened dry box, 5.0 mmol (1.45 g) of the ligandmade in Example 1 were charged to a 100 ml Schlenk tube equipped with astir bar. The ligand was dissolved in 5 ml of toluene. To a secondvessel equipped with a stir bar was charged 5.5 mmol (2.5 g) tetrabenzylzirconium and 10 ml toluene.

The ligand solution was transferred into the tetrabenzyl zirconiumsolution. The vessel was covered with foil and allowed to stir at roomtemperature in the dry box. After 6 hours at room temperature 80 ml dryhexane was added to the reaction solution and allowed to stir overnight.The reaction mixture was filtered through a medium porosity frit withapproximately 2 g pale yellow solids collected.

Example 3

In a dry box, MMAO type 3A (5.8 mLs, 10 mmoles, 1.74M, 6.42 wt % inheptane) was charged to an oven dried, 4 dram glass vial.2-methyl-1-phenyl-2-propanol (15.5 μLs, 0.1 mmoles) was added to theMMAO dropwise while stirring resulting in a clear solution.

In a dry box, toluene (0.1 mLs, alumina dried) was charged to an ovendried, 4 dram glass vial. The complex prepared in Example 2 (0.5 μmoles,6.3 microliters of an 0.080M solution in toluene) was added to the1-hexene resulting in a pale yellow solution. TheMMAO/2-methyl-1-phenyl-2-propanol solution prepared in the paragraphabove (0.25 mmoles, 0.13 mL) was then added to the vial resulting inpale yellow reaction solution. The vial was heated in an oil bath at 50°C. for 5 minutes resulting in a reddish brown reaction solution.

The reaction solution was charged to a 1-L slurry reactor containing 600mLs n-hexane, 43 mLs 1-hexene, and 0.13 mLs (0.25 mmoles)MMAO/2-methyl-1-phenyl-2-propanol solution, and run at 85° C. and 85 psiethylene for 30 minutes. The reaction produced 16.3 g of polyethyleneresin (activity=76706 g polyethylene/mmole Zr/hour/100psi ethylene,I2=0.069, I21=2.15, MFR=31.1, BBF=7.71). Size Exclusion Chromatography(SEC) revealed the following molecular weight properties: Mn=54,637,Mw=292,411, PDI=5.35.

Example 4

In a dry box, MMAO type 3A (5.8 mLs, 10 mmoles, 1.74M, 6.42 wt % inheptane) was charged to an oven dried, 4 dram glass vial.2-methyl-1-phenyl-2-propanol (15.5 μLs, 0.1 mmoles) was added to theMMAO dropwise while stirring resulting in a clear solution.

In a dry box, toluene (0.1 mLs, alumina dried) was charged to an ovendried, 4 dram glass vial. The complex prepared in Example 2 (0.5 μmoles,6.3 microliters of an 0.080M solution in toluene) was added to thetoluene resulting in a pale yellow solution. TheMMAO/2-methyl-1-phenyl-2-propanol solution prepared in the paragraphabove (0.25 mmoles, 0.13 mL) was then added to the vial resulting inpale yellow reaction solution. The vial was heated in an oil bath at 50°C. for 15 minutes resulting in a reddish brown reaction solution.

The reaction solution was charged to a 1-L slurry reactor containing 600mLs n-hexane, 43 mLs 1-hexene, and 0.13 mLs (0.25 mmoles)MMAO/2-methyl-1-phenyl-2-propanol solution, and run at 85° C. and 85 psiethylene for 30 minutes. The reaction produced 13.2 g of polyethyleneresin (activity=62118 g polyethylene/mmole Zr/hour/100 psi ethylene,I2=0.248, I21=7.85, MFR=31.6, BBF=6.30). Size Exclusion Chromatography(SEC) revealed the following molecular weight properties: Mn=42,411,Mw=205,990, PDI =4.86.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures. As isapparent form the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly it is not intended thatthe invention be limited thereby.

What is claimed is:
 1. A process to polymerize olefins comprisingcontacting an olefin with a catalyst composition comprising the reactionproduct of an activator, an additive and a transition metal compoundrepresented by the formulae: ((Z)XA_(t)(YJ))_(q)MQ_(n) wherein M is ametal selected from a group consisting of Group 3 to 13 transition metaland lanthanide and acti mide series of the Periodic Table of Elements; Qis bonded to M and each Q is a monovalent, divalent or trivalent anion;X and Y are bonded to M; X and Y are independently carbon or aheteroatom, provided that at least one of X and Y is a heteroatom; Y iscontained in a heterocyclic ring J, wherein J comprises from 2 to 50non-hydrogen atoms, Z is bonded to X, wherein Z comprises 1 to 50non-hydrogen atoms; t is 0 or 1; when t is 1, A is a bridging groupjoining X and J, q is 1 or 2; n is the oxidation state of M minus q if Qis a monovalent anion, n is (the oxidation state of M−q)/2, if Q is abivalent anion or n is (the oxidation state of M−q)/3 if Q is atrivalent anion, optionally R′_(m) may be bound to Z and/or R″_(p) maybe bound to J the R″ groups are independently selected from the groupconsisting of hydrogen or linear, branched, cyclic, alkyl radicals, oralkenyl, alkynyl, alkoxy, aryl or aryloxy radicals, two or more R″groups may be joined to form a cyclic moiety, m is an integer from 0 to5; the R′ groups are independently selected from group consisting ofhydrogen or linear, branched, alkyl radicals or cyclic alkyl, alkenyl,alkynyl or aryl radicals; two or more R′ groups may be joined to form acyclic moiety, p is an integer from 0 to 5, preferably 2, and whereinthe additive is an alkoxy compound.
 2. The process of claim 1 whereinthe alkoxy compound is one or more of acetone, benzophenone, methylethyl ketone, diethyl ketone, methyl isobutyl ketone, methyl isopropylketone, diisopropyl ketone, methyl tertiary butyl ketone, acetophenone,cyclohexanone, cyclopentanone, benzaldehyde, pivaldehyde, ethyl n-propylketone, or ethyl isopropyl ketone.
 3. The process of claim 1 wherein Mis zirconium.
 4. The process of claim 1 wherein each Q is independentlyselected from the group consisting of halogens, hydrogen, alkyl, aryl,alkenyl, alkylaryl, arylalkyl, hydrocarboxy or phenoxy radicals having1-20 carbon atoms, amides, phosphides, sulfides, silylalkyls,diketonates, and carboxylates.
 5. The process of claim 1 wherein X and Yare independently nitrogen, oxygen, sulfur or phosphorus.
 6. The processof claim 1 wherein Z is an aryl group.
 7. The process of claim 1 whereinJ is pyridine.
 8. The process of claim 1 wherein the transition metalcompound is [1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-DiisopropylphenylAmido] Zirconium Tribenzyl and the additive is acetone.
 9. The processof claim 1 wherein the activator is an alumoxane.
 10. The process ofclaim 1 wherein the activator is a non-coordinating anion.
 11. Theprocess of claim 8 wherein the activator is an alumoxane.
 12. Theprocess of claim 8 wherein the activator is a modified methyl alumoxane.13. The process of claim 11 wherein the olefin is a monomer having 2 to30 carbon atoms.
 14. The process of claim 1 wherein the olefin comprisesethylene.
 15. The process of claim 1 wherein the olefin comprisesethylene and one or more of propylene, butene-1,pentene-1,4-methyl-pentene-1, hexene-1, octene-1, decene-1, and3-methyl-pentene-1.
 16. The process of claim 1 wherein the process takesplace in the gas phase.
 17. The process of claim 16 wherein the catalystcomposition is fed into the reactor as a solution.
 18. The process ofclaim 16 wherein the transition metal compound is[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl Amido]Zirconium Tribenzyl, the additive is acetone and the activator is analumoxane.
 19. The process of claim 16 wherein the catalyst compositionfurther comprises a metal stearate.
 20. The process of claim 1 whereinthe process takes place in the slurry phase.
 21. The process of claim 20wherein the catalyst composition is fed into the reactor as a solution.22. The process of claim 20 wherein the catalyst composition is fed intothe reactor as a slurry.
 23. The process of claim 20, wherein thetransition metal compound is[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl Amido]Zirconium Tribenzyl, the additive is acetone and the activator is analumoxane.
 24. The process of claim 20 wherein the catalyst compositionfurther comprises a metal stearate.
 25. The process of claim 20 whereinthe catalyst composition further comprises aluminum distearate.
 26. Theprocess of claim 1 wherein the additive is combined with the transitionmetal compound in the reactor.
 27. The process of claim 1 wherein thetransition metal compounds are contacted with solvent prior to contactwith the activator.
 28. The process of claim 1 further comprising amethod to control molecular weight distribution (Mw/Mn), flow index,and/or density comprising altering on line in a gas phase reactor havinga volume of 1500 cubic feet or more the reaction temp and/or thehydrogen concentration and/or the activator to transition metal ratio.